Azo dyes containing an imidoethylsulfonylethyl group



United States Patent Oflice 3,394,121

Patented July 23, 1968 ethyl; lower carballcox alk l, e. carhethox eth 1; halo- 3,394,121 y y y y genoalkyl, e.g., chloroethyl; hydroxyhalogenoalkyl, e.g.,

AZO gg fi-hydroxy-m-chloropropyl; lower alkylsulfonylalkyl, e.g., Max A. Weaver and John I Dale m, Kingsport, Tenn, methylsulfonylethyl; lower alkyl-OCOCH CH e.g., assignors to Eastman Kodak Company, Rochester, N.Y., 5 CHeOCOOCHZCHZ; carbamoylalkyl carbamoyl' acorporation of New Jersey ethyl; lower alkylcar-bamoylalkyl, e.g., ethylcarbamoyl- No Drawing. Filed Oct. 22, 1965, Ser. No. 502,430 ethyl y p y y a, B-p y y lower 9 Claims. (Cl. 260-152) alkylsulfonamidoalkyl, e.g., methylsulfona-midoethyl; di-

carboximidoalkyl, e.g., fl-dicarboximidoethyl, etc. or R 10 represents a monocyclic carbocyclic aromatic radical of ABSTRACT OF THE DISCLOSURE the benzene series, e.g., unsubstituted phenyl and sub- Phenyl azo aniline compounds containing a dicarbox stituted phenyl such as represented by R above e.g., lower imidoalkylsulfonylalkyl group attached to the aniline alkylphenyl lower alkoxyphenyl halophenyl A preferred group represented by R includes hydrogen, alkyl, gg gfgi are useful as dyes for hydrophoblc textlle alltoxyalkyl, phenoxyalkyl, alkanoyloxyalkyl, haloalkyl,

hydroxyalkyl, carbethoxyalkyl or cyanoalkyl, the alkyl groups of which are lower alkyl. As can be seen from This invention relates to novel water insoluble azo the examples given below, the sllbstilueflts attached to compounds and, more particularly, to azo compounds, the R, R1 and R2 groups Serve p y as auxochfome such as azo dyes, containing an imidoethylsul-fonylethyl groups to control e 1 the eompeundgroup R represents a dicarboximido radical, e.g., a radical The azo dyes of the invention are characterized by the havlng the formula general formula 00 /R2 N\ /Z R-N=N-R N oo Q H Q Q H -Ra (I) wherein Z represents a substituted or nonsubstituted hydrocarbon radical or group of carbon atoms necessary to wherein R represents a monocychc carbocychc aromatic complete the cyclic imide, Such as alkylene radical of the benzene series, e.g., phenyl and substituted phenyl having the formula (--CH CH Q vinylene (-CH=CH); o-phenylene, e.g.,.

wherein X may be lower alkyl, e.g., methyl; lower alkoxyl, e.g., methoxyl; halogeno, e.g., chlorine; nitro; lower alk lsulfon l, e.g., methylsulfonyl; lower alk lsulfonamido, e.g., i'nethylsulfonamido; dicarboxylic acid hydroxyalkylene; lower alkanoyloxyalkylene imido, e.g., succinimido; lower fluoroalkyl, e.g., trifluoro- 4 toxyethykne; cycloalkylene hexalpethylene; cyano" methyl; lower alkanoylamino, eg acetamido; cyano; alkylene, e.g., cyanoethylene; haloalkylene, e.g., chlorocarbamoyl; benzamido; thiocyano; lower alkylthio, e.g., ethylene and the like th i 1 1k The novel azo dyes of the invention, characterized 3 2 5 323 gzf g fizgfigtf gg gg ggg f T s g by Formula I above, are prepared by coupling a convencarbalkoxy, carbethoxy; benzoyl and the like and tional diazomum salt of a compound having the formula (11) may be 0, 1, 2 O1 3; I R NHZ (H) R represents a monocychc carbocyclic aromatic rad1- cal of the benzene series, e.g., phenylene and substituted with a coupling component having the formula phenylene having the formula R2 C gl-LS O 2 C zHr-R (III) Y(m) wherein R, R R and R are defined above. wherein Y may be lower alkyl, eg methyl; lower Thus, the schematic reaction is illustrated as follows: oxyl, e.g., methoxyl; halo, e.g., chloro; alkylsulfonyl, dmzotimion e.g., methylsulfonyl; lower alkylsulfonamido, e.g., meth- R-NH: diazonium salt ylsulfonamido; dicarboxylic acid imido, e.g., succinimido; (II) lower alkanoylamino, e.g., acetamido; benzamido; thio- 2 cyano; lower alkylthio, e.g., methylthio; benzoxyl; benzl:{LN/ amino; benzylamino; N-alkylbenzylamino, e.g., N-phenylmethylamino; carbalkoxy, e.g., carbethoxy; benzoyl and 2 2 4R the like and (m) may be 0, 1 or 2; (III) R represents hydrogen or an alkyl radical including unsubstituted alkyl, preferably lower alkyl, e.g., from 1 I! to 4 carbon atoms, and substituted alkyl such as hydroxyalkyl, e.g., hydroxyethyl; polyhydroxyalkyl, e.g., 2,3- dihydroxypropyl; lower alkoxyalkyl, e.g., methoxyethyl; oyanoalkyl, e.g., cyanoethyl; cyanoalkoxyalkyl, e.g., B- CzH4SO2C2lL|-R3 cyanoethoxyethyl; lower alkanoyloxy alkyl, e.g., acetoxy-- (1) 3 The coupling components, represented by Formula III above, are prepared by the reaction of an alkylor aryldicarboximide with a vinylsulfonylethylaniline derivative, the reaction being schematically illustrated as follows:

wherein R, R R and R are defined above.

The preparation of the coupling components and the dyes produced therefrom will be more fully illustrated by the following examples.

EXAMPLE 1 (a) Preparation of the coupler.-One ml. of 40% aqueous Triton B was added to a stirred slurry of 7.35 g. phthalimide, 0.5 g. hydroquinone and 25 ml. dioxane. A solution of 12.65 g. of N-fi=vinylsulfonylethyl-N-ethylm-toluidine (prepared by the reaction of N-ethyl-m-toluidine with divinylsulfone in acetic acid) in 15 ml. dioxane was added dropwise during 15 minutes. The reaction mixture was stirred and heated at reflux for 2 /2 hours then drowned in water. The solid which formed was crystallized from ethanol. It melts 1l711'8.

Analysis.-Calcd.: C, 63.0; H, 6.0; N, 7.0. Found: C,

63.19; H, 6.06; N, 6.80. It has the structure:

(1)) Preparation of the dye.An amount of 6.9 g. p-nitroaniline was dissolved in 5.4 ml. conc. sulfuric acid and 12.6 ml. H O. This solution was poured onto 50 g. of ice and then a solution of 3.6 g. sodium nitrite in 8 ml. of water was added all at once. The diazotization was stirred at for 1 hour, resulting in almost complete solution. After filtration, the diazonium solution was added to a chilled solution of 20.0 g. of the coupler prepared in (a) above, in 100ml. 1:5 acid (1 part propionic acid:5 parts acetic acid). The coupling was neutralized with solid ammonium acetate to brown on Congo red paper and allowed to couple 1 hour. It was drowned in water, filtered, washed and dried. The product dyes polyester and cellulose acetate fibers bright orange shade with excellent fastness to light and sublimation. It has the structure:

All of the couplers were prepared in accordance with the procedure of Example 1 with substitution of appropriate alkylor aryl-dicarboximide and vinylsulfonylethylaniline compounds.

4 EXAMPLE 2 An amount of 6.9 g. p-nitroaniline was diazotized as in Example 1 (b). This diazonium solution was added to a chilled solution of 22.2 g. of N-B-acetoxyethyl-N-[2-(2- phthalimidoethylsulfonyl)ethyl]aniline in 150 ml. of 1:5 acid. This was neutralized with solid ammonium acetate to brown on Congo red paper and allowed to couple 2 hours, all at 510 C. The reaction was then drowned with water and the product collected by filtration, washed with water, and air dried. It dyes polyester fibers bright shades of orange with excellent fastness properties. It has the structure:

A solution of 0.72 g. dry NaNO in 5 ml. conc. H 50 was cooled in an ice bath, and 10 ml. 1:5 acid was added below 15 C. This solution was stirred at 5 C. and 1.72 g. of 2-chloro-4-nitroaniline was added, followed by 10 ml. 1:5 acid. The diazotization was stirred 2 hr. at 05 C., then added to a chilled solution of 4.0 g. of N-ethyl- N- 2- 2-phthalimidoethylsulfonyl ethyl] m-toluidine in 25 ml. 1:5 acid. This coupling was kept at below 10 C. and neutralized to brown on Congo red paper by the addition of solid ammonium acetate. After coupling 2 hr., the mixture was drowned in water, filtered, washed with water and dried at room temperature. The product dyes polyester fibers a deep shade of red with good fastness properties. It has the structure:

An amount of 6.9 g. 2,6dichloro-4-nitroaniline was dissolved in 37.5 ml. conc. H at about 25 C. The solution was chilled and a solution of 2.2 g. NaNO in 15 ml. conc. H 50 added below 5 C. The diazotization was stirred at 05 C. for 2 hr. then added to a chilled solution of 10.5 g. of N-ethyl-N-[Z-(Z-succinimidoethylsulfonyl)ethyl]m-toluidine in ml. of 15% H 80 The coupling was neutralized to brown on Congo red paper, keeping the temperature below 10 C., by the addition of solid ammonium acetate. After coupling 2 hr., the mixture was drowned with water, filtered, washed with water, and air dried. The product dyes polyester fibers a desirable shade of brown having excellent fastness properties. It has the structure:

EXAMPLE 5 idine as the coupler. The dye imparts brown shades to 5 polyester fibers and has the structure:

ized with solid ammonium acetate to brown on Congo red paper, at less than C. After coupling 2 hr., the mixture was drowned with water, filtered, washed, and air dried. The product dyes polyester fibers a pink shade with excellent light and sublimation fastness. It has the structure:

0 0 CgHn g OZHE C oiN- N=N N\ OzN--N-N-N\ (ll 7 C2H4SO2C2H4N 10 C2H4SO2CzH4N 1 Ha S 2C a 0 21 1 5 ll EXAMPLE 6 In accordance with Examples 1 through 6, additional dyes were prepared correspondmg to the formula An amount of 0.72 g. dry NaNO was added portionwise to 5 ml. cone. H 80 and the solution cooled. To this was added 10 m1. 1:5 acid followed by 2.16 'g. Z-methyl- N=NR N CO sulfony1-4-nitroaniline and 10 ml. more 1:5 acid, all at \C2H4SO2CBHPN/ 0-5" 0. The diazotization was stirred at 05 C. for 3 X hr. and then added to a chilled solution of 4.0 g. of 00 N ethyl N [2 (2 phthalimidoethylsulfonyl)ethy wherein X, R R and Z are set forth in the following m-toluidine in ml. 1:5 acid. The couphng was neutraltabl TABLE Example No. X R1 R2 Z Color 7 p-NOr m-Tolylene C2H5 Orange.

3 [I -N02 10 -C2II4CN ?H2 'H0.

9 p-NO: .....do 'CHzCHzCl /(CH )3 D0.

CHOH 1U DNOZ .----d0 -CHzCHzOOHa D0.

"CH: 11 p-N01 .d0 -CHzCHzOCOCH3 -CHOCOCH3 D0.

(3 0 CH2 -OH2 D0. 12 p-NOz do -CH2OH2 I o 0 on,

13 IJNOQ .d0 -CH2CH2CO2C2H5 D0.

14 p-NOa .do -cmomnr Do. 15 p-NOQ d0 "CHIGH2SO2CH3 ?HCH3 D0.

*CHCHs 16 -N01 .d0 CH;CH;CONH2 -|CHC1 D0.

CH2 C0\ CHg 17 p-NOr do 43112011211 Do.

HCHa 00 0H, 18 p-NO; do o1-nomoo0m1 Do.

CHCN 19 211014-01 do -o1rr. Red.

TABLE-Contim1ed Example No. X R1 R2 Z Color 20 2-NO2-4-C1 m-Tolylene c1IZcn2011 Scarlet.

21 2-NU -4-Cl Phuuyluuu u -0u2011,c1 D0.

22 4-NO -2-Ol m-Tolylunu -CI17C1I2N Do.

23 4-NO2-2-C1 Phunylene C;I-I5 D0.

24 2,6-di-Cl-4-NO2 m-Tolylenu C;;II5 Yellow-brown.

25 2,G-diCl-4-NO2 .mdo 431114011 D0.

26 Q-CHaSOz-l-NO; d0 7 V 4 C2Hn Red-violet.

27 Z-CH SO A-NO; .110 -CzH Cl Do.

28 None ..d0 -C2H5 Yellow.

29 .410 Phouylone -CH2OHOH Do.

30 .110 d0 -OH;C1I2C1 1 Do;

31 p-CH3S01 m-Tolylouu CZH5 -3 Orange.

32 H D-CHgSOz V d0 CHzClI2C1 1 Yellow-orange.

3;; -uugsog u lulyluuu -u -i Yellow.

34 1-01-1300 m-Tolyluue C;I-I5 Do.

I II I TABLIE-Alontlnued I I I I I I I Example No. I X R1 I II I R2 I ZI Color a5 p-Cl m-Tolylene -c mcmon Yellow.

3s p-Ol -do -CH2CH2N Do.

37 p-Ol .d0 -cmomocoz-m Do.

as p-CN .mdo 42H, D0.

39 p-NO m-Chlorophenylene 43211, D0.

40 p-NO; o-Chlorophenylene H D0 41 2,4-di-CH3SO m-Tolylene -C2H Red;

42 ,4-(1i-CII5SO; ....a0 CHnCHzOH -3 Red.

43 2,4-ai-omso2 .do CH2CHgOCONH Red.

44 2,4-ai-cms02 undo -Q CHCHN\ IL Red.

45 2,4-di-CH SOZ Phenylenc 432m Red.

40 2,4-(11-0113302 o-Tolylene -H Red;

47 p-CH m-Tolylone C2H5 Yellow.

48 V. -om ..d0 -CH4Cl Do.

49 om Phenylene -CH4OH Do.

'DABLE--Continued Example No. X R R Z Color p-SONIh Phenylene C2H Red.

51 -somn, n1T0l,v10ue H 432m; Rod.

52 -cn "do c,m T Yellow.

53 p-NO 2-0CH35-1nethylphenylene C;H Violet.

54 p-NO; d0 C=H4OH -3 D0.

55 p-NO 2-0CH3-5-NHCOCH3 pl10r1y10ne C;H T D0.

56 p-SOzN(CH3);| mT01ylene -c,H, Red.

51 2,4-di-NO -6-Cl .do 43,116 Violet.

58 4-CH3SOz-2-C1 .d0 CzH Orange-yellow,

so 4-cms0r2-c1 d0 -c11,cH,0H D0.

60 "44311300 201 1o --c1n5 D0.

61 4-CHO do 412m Orange,

C Hr-C O 62 4- N .dO C:H5 Yellow.

C HaC O H Orange. p-NO; Phenylene C;H4O C C H;

64 2,6-d1ch10r0-4-NO1 m-Tolylene --C;H5 -CH; Brown.

The azo compounds of the invention can be used for dyeing textile materials including protein and synthetic polymer fibers, yarns and fabrics giving a variety of fast brilliant violet to yellow shades, including red, orange, yellow, brown and violet when applied thereto by conventional dye methods. The azo compounds have good atfinity for cellulose ester and polyamide fibers. When the azo compounds are used for dyeing such hydrophobic materials, they should be free of water-solubilizing groups such as sulfo and carboxyl. In general, the dyes have excellent fastness, for example, to light, washing, gas (atmospheric fumes) and sublimation.

As described above, the present azo compounds are characterized by an imidoethylsulfonylethyl group. This distinctive structure imparts unexpected properties to the present azo compounds, especially when the azo compounds are used for dyeing textiles, including improved fastness to light and improved affinity for polyester fibers. Thus, the azo compounds of the invention can be expected to be superior to similar but distinct dyes when tested by methods such as described in the A.A.T.C.C. Technical Manual, 1964 edition, depending in part upon the particular dye used and the fiber being dyed.

The azo compounds of the invention may be used for dyeing hydrophobic fibers such as linear polyester, cellulose ester, acrylic, polyamide, etc., fibers in the manner described in U.S. Patents 2,880,050, 2,757,064, 2,782,187 and 2,943,827. The following examples illustrate methods by which the azo compounds of the invention can be used to dye polyester textile materials.

0.1 g. of the dye is dissolved in the dye pot by warming in cc. of ethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurate and 0.5% sodium 'lignin sulfonate aqueous solution is added, with stirring until a fine emulsion is obtained. Water is then slowly added to a total volume of 200 cc., 3 cc. of Dacronyx (a chlorinated benzene emulsion) are added and grams of a textile fabric made of Kodel polyester fibers are entered. The fabric is worked 10 minutes without heat and then for 10 minutes at 80 C. The dye bath is then brought to the boil and held at the boil for one hour. Following this, the fabric is rinsed in warm water, then scoured in aqueous 0.2% soap, 0.2% soda ash solution. After scouring, the fabric is rinsed with water and dried. Accordingly, since the azo compounds of the invention are water-insoluble, they can be applied from aqueous dispersions in the manner of the so-called dispersed dyes. However, coloration can also be effected, for example, by incorporating the azo compounds into the spinning dope and spinning the fiber as usual. The azo compounds of the invention have varying utility as dyes. The degree of utility varies, for example, depending upon the material being dyed and the formula of the azo compound. Thus, for example, all the dyes will not have the same degree of utility for the same material. For example, the substituents on the R, R and R radicals, as mentioned above, se-rve primarily as auxochrome groups to control the color of the azo compound.

Polymeric linear polyester materials of the terephthalate type are illustrative of the linear aromatic polyester textile materials that can be dyed with the new disazo compounds of our invention. The terephthalate fibers sold under the trademarks Kodel, Dacron, and Terylene, for example, in the form of filaments, yarn and fabric for example, are illustrative of the polyester textile materials that can be dyed. Kodel polyester fibers are more particularly described in U.S. Patent 2,901,446. Dacron and Terylene polyester fibers are described, for example, in U.S. Patent 2,465,319. The polymeric linear polyester materials disclosed in U.S. Patents 2,945,010, 2,957,745 and 2,989,363 for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C.

Nylon, in fiber, yarn and fabric form, is representative of polyamides which can be dyed with the azo compounds.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described above and as defined in the appended claims.

What we claim is:

1. A water-insoluble azo compound having the formula X represents lower alkyl, lower alkoxyl, chlorine,

bromine, nitro, lower alkylsulfonyl, lower alkylsulfonamido, succinimido, trifiuormethyl, lower alkanoylarnino, cyano, carbamoyl, benzamido, thiocyano, lower alkythio, formyl, acetyl, lower carbalkoxy, sulfamoyl, or dimethylsulfamoyl;

n represents 0, 1, 2 or 3;

Y represents lower alkyl, lower alkoxyl, chlorine,

bromine, lower alkanoylamino, lower alkylsulfonamido, lower alkylthio, or benzamino;

m: represents 0, 1 or 2;

R represents hydrogen; lower alkyl; lower alkyl substituted with hydroxy, lower alkoxyl, cyano, lower alkanoyloxy, lower carbalkoxy, chlorine, bromine, lower alkylsulfonyl, lower alkyl-OCDO-, carbamoyl, phenoxy, phenylcarbamoyloxy, succinimido, phthaimido, or lower alkylsulfonamido; benzyl; phenyl; or phenyl substituted with lower alkyl, lower alkoxy, chlorine, or bromine; and

Z represents alkylene of 2 or 3 carbon atoms; alkylene of 2 or 3 carbon atoms substituted with hydroxy, lower alkanoyloxy, cyano, chlorine, bromine, or methyl; vinylene; o-phenylene; 1,2-cyclopentylene; or 1,2-cyclohexylene.

2. A water-insoluble azo compound having the formula X represents nitro, chlorine, bromine, lower alkylsulfonyl, cyano, or trifluoromethyl;

n represents 1, 2, or 3;

Y represents lower alkyl, lower alkoxy, chlorine bromine, or lower alkanylamino;

m represents 0, 1, or 2;

R represents lower alkyl or lower alkyl substituted with lower alkoxy, phenoxy, lower alkanoyloxy, chlorine, bromine, hydroxy, carbethoxy, or cyano; and

Z represents alkylene of 2 or 3 carbon atoms, vinylene,

or o-phenylene.

3. A compound according to claim 2 wherein X represents nitro, chlorine, bromine, methylsulfonyl,

or cyano;

n represents 1, 2, or 3;

Y represents lower alkyl;

m represents 0 or 1;

R represents lower alkyl or lower alkyl substituted with chlorine, bromine, hydroxy, or lower alkanoyloxy; and

Z represents ethylene or o-phenylene.

15 4. The dye:

CzHs

5. The dye:

6. The dye:

7. The dye:

8. The dye:

C1 CzHu g O N N N/ 2 C O CzH4SOzC2H4N I? O CZH4OH7CH3 H O C2II4SOzC2H4N The dye:

O CzH4SOzC2H4N H SOHOHS CH3 0 n O 0 '5 References Cited UNITED STATES PATENTS 02155 0 2,816,101 12/1957 Breig et a1 260 152 XR 1! CH 3,096,322 7/1963 Straley et a1. 260-152 XR 2 3,148,178 9/1964 Wallace et a1. 260152 C2H4S02C2H4N\ 3,148,180 9/1964 Straley et a1. 260-152 XR FLOYD D. HIGEL, Primary Examiner. 

